Water soluble metallic organic compound and process of making the same



I carbon atom and is of that group of metals,

- Patented June 22, 1926.

UNITED STATES, PATENT o-Fnca.

Application fled April 24,1924. Serial are. 708,807.-

The present'invention relates to the prosolution. The phenyl more chloride is duction of water soluble organo-metallic then added to the'solution m a ut the procompounds, and particularly of such comportion of one mol of the latter to one and pounds in which the metal is bonded to a one-quarter mols of potassium thioglycollate in solution. The mixture is gently warmed, preferably with agitation, and the mercury compound pases readily into solution,-ap-

: No Drawing.

including mercury, arsenic, antimony and bismuth, which, having a valence greater than 1, form stable organo-metalliccompounds with the metal bonded to a carbon atom.

' The invention is of particular importance in connection with the organic compounds having germicidal or therapeutic value, such as compounds of mercury, arsenic, antimony, bismuth and the like, the efliciency of which have hitherto been greatly limited by the difiiculty of producing r'eadily soluble compounds.

In carrying out the process of my invention I react upon an organo-metallic compound with a water soluble compound containing the thio hydroxyl group (SH), of which the mercaptans are the simplest examples. Thus I may use thioalcohols such as ethyl mercaptan, thioglycerine or thiO.

glycol, or their carboxylic or sulfonic compounds, such as thioglycolic acid, thiolactic acid, thiomalic acid, thiosalicylic acid, etc.; thiophenols, such as thioresorcinol, thiona hthol and like products.

typical formula for the organo-metallie compounds is as follows: R--Hg-w in which R is any organic radical having the Hg attached to a carbon atom and in. which an is any replaceable inorganic radical or group. Hg can be replaced by any metal having a valence greater than one which will form organo-metallic compounds with the metal bonded to a carbon atom and which com ounds are stable toward water. These meta are in general those lying lower than hydrogen in the'electromotive series.

The following specific examples illustrate the invention:

.Ezample 1. Phenyl mercury chloride, C,H,,.-Hg0l, is tre ted with HS .CQOK. The potassium thio lysome, which is watersoluble, is first solved in water, preferably as. a concentrated potassium th1o-glycol1ate,

The addition parently as the compound having the formula The follc fling reaction takes place C,H,HgCl +HS OH, COOK C.H Hg- SOIL:- COOK HCl To neutralize the hydi' chloric acid resulting from the above reaction the requisite amount of sodium bicarbonate, NaHGO,

may be added to'the solution. To purify the product thus formed, hydrochloric acid or any other acid may be added. A white precipitate is formed which is c mn -s-cm-coon.

This substance melts, with decomposition, at-

164 C. This may be collected on a filter, washed well with water to remove any .inorganic salts, dried in a dessicator and then dissolved in the calculated amount of sodium orpotassium hydroxide and the whole poured into alcohol. The salt separates and is collected on a filter. This of small amount of if carbonate is quite beneficial for it neutralizes the hydrochloric acid formed in the reaction.

The compound thus obtained, namely separates which can be collected on a filter andlzashedfree from all impurities. The precipitate can then be dissolved in the 'calculated amount of a sodium hydroxide solution and the latter poured into 95% alcohol. The product on 0.1a. Est 01, 2 its on,

The alcoholic solution is then evaporated to dryness in vacuo. The residue is treated antimony compound given in Example 3,

' the later definite p with water and then a small amount of acetic 1 acid is added. The precipitate thus obtained is washed well with water and collected on the filter and then dissolved in the concentrated solution of one equivalent of sodium hydroxide and. the whole poured into a mixture of alcohol and ether. The following salt separates:

- (CH, o.H. .Esb= s-0H, 000m The com 0nd thus obtained is soluble in water, inso able in alcohol ether mixture, insoluble in benzene and other common organic solvents. Upon boilin for a long time in water the solution is roken down. It has no melting point.

Ewample 4. To an alcoholic solution of phenyl arsenious chloride an equivalent amount of'the per ed tassium salt of thioglycollic acid is ad and the Whole warmed for about five minutes on a water bath. The following compound is produced:

. 3,H, As= c1, +2 HS on, COOK-v can As= e011,. c'ooK ,+2Hc1 The compound can be purified'in exactly the same 'manner as outlined in case of the and namely the formation of'the free as?l It as no reparation of the salt. 7 ysical characteristics.

It is insoluble in most organic solvents;

.has no definite melting point and decomposes upon long boiling in water solution or with mineral acids.

Minor changes may emade in the steps COO K- vents. tnne, particularly -1Il concentrated solution,

7 mercuric sulfide separates. The free acid of this salt may be-obtained by the addition of any strong acid.

E arample 3.

To an alcoholic solution of p-tolyl antimony chloride the equivalent amount of sodium or potassium salt of thioglycollic acid is added and the whole warmed for five minutes on a water bath. The following compound is produced:

C H ESb= (8- CH, COOK) +2HCl of the process within the scope of the appended claims without departing from t e spirit of the invention.

I claim:

1. The process of producing water soluble metallo-organic compounds which comprises treating with a solution of an or ganic compound containing a thio-hydroxyl group a compound of the formula RMas in which R is any organic radical having the metal attached to a carbon atom, in which a: is any replaceable inorganic radical or group, and in which M is anymetal having a valence greater than one which will form crgano-metallic compounds with the metal bonded to a carbon atom, stable toward water.

2. The method of producing a water soluble metallo-organic compound which com,- prises treating with a solution of a salt of an organic thio-hydroxyl compound containing an acid group of the formula R-Mw in which R is any organic radical having the metal attached to a carbon atom,

\Vhen cooled for a long period of in which w is any replaceable inorganic radical or group, and in which M is any metal having a valence greater than one which will form organo-metallic compounds with the metal bonded to a carbon atom, stable toward water. 1

3. The method of producing a water soluble metallo-organic compound which comprises treatinguan organo mercuric compound having the formula R- -Hg.-a: in which R is any organic radical having the Hg attached .to a carbon atom "in which a; is any replaceable inorganic radical or group with a solution of an organic thiohydroxyl compound.

4. The method of producing a. water soluble metallo-organic compound which comprises treating an organo 111810111'10 compound having the formula R-Hg-fl in,

which R is any organic radical having the Hg attached to a carbon atom in which a: is any replaceable inorganic radical or group with an alkaline solution of a thio-hydroxyi organic acid. v

5. A water soluble salt of the following acid RHg.S.CH COOH in which R is an organic radical having the mercury directly attached to a carbon atom.

6. A water soluble salt of a compound of the following general formula in which R is any organic radical group, R is an organic radical containing an acid group, M is a metal of a group forming confpounds stable toward water with the metal bonded to a carbon atom of an organic group and having valence greater than 1,

and n is an integer greater than 0' and atleast one less than the valence of the metal,

the metal and the sulphur in the compound being bonded to the carbon atoms of the groups R and R respectively. tr

7. A water soluble salt of a compound of mercury of the following general formula R,.I-Ig-SR in which R is any aromatic or aliphatic group, R is an organic radical containing an acid group, the'Hg and S atoms being bonded to carbon atoms of the B group and R group respectively.

8. The process of producing a water soluble -mercuri organic compound which comprises treating an organic compound of mercury of the formula RHga;'-in which R is any organic "radical having the mercury attached to a carbon atom and in which a5 is any replaceable radical or group with a water solution of an alkali metal salt of thio-glycolic acid.

9. The process of producing a water soluble mercury organic compound which comprises treating phenyl mercuric chloride with a water solution'of an alkali-metal salt of thio-glycolic acid.

I MORRIS SELIG KHARASCH. 

